Warp sizing process



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WARP SIZING PROCESS Herbert C. Olsen, Berkeley Heights, N.J., assignor to National Starch and Chemical Corporation, a cargo ration of Delaware No Drawing. Filed Aug. 26, 1958, Ser. No. 757,191

6 Claims. (Cl. 117-1395) This invention relates to a method for the warp sizing of textile yarns and to the improved textiles thus obtained. More specifically, an object of this invention is to provide a stable, uniform sizing material which may be applied to yarn prior to the weavingprocess, thereby imparting greater tensile strength, additional: compactness, smoothness and improved resistance to abrasion. A further object is to facilitate the weaving process by strengthening the yarn in this manner.

Another. object of this invention is to decrease the quantity of sizing required for the weaving process, thus reducing costs and increasing the speed and efiiciency of the operation, without any deterioration in the overall quality of the resulting textiles.

As used in this invention, warp is an inclusive term which refers to the lengthwise running yarns in a woven fabric. A warp sizing material is any substance which is applied to the warp yarns for the basic purpose, as ex-- plained above, of strengtheningthese yarns, usually as a resultv of its adhesive, film forming action.v

The warp sizing, or splashing as itis often called, of textile yarns consists in the impregnation of these yarns with a sizing solution or dispersion. This is followed by removal of the excess sizing by passage of the Wet yarns through a set of squeeze rolls followed by drying.

Warp sizing is carried out on a splashing machine consisting of a creel which generally holds one or more section beams. These section beams usually contain from 200500 yarn ends. The yarn ends from several of these section beams are brought together so as to form a sheet of yarn with about 1500-8000 ends. This. sheet then enters the size box wherein it is guided through the sizing solution and through one or more sets of squeeze rolls, so as to remove the surplus size which'thenfalls back into the size box. Drying is accomplished by pass ing the yarn through a heated chamber or over the surface of internally heated drying cylinders (cans).

The dried yarn is then separated by means'of horizontal split rods into sections corresponding to those of the original section beams. The yarnv is then almost immediately recombined by being passed throughv a vertical comb and thereuponontoa take-up beam referred to asa loom beam. This loom beamholds the yarn until such timeas it is used in the weaving process.

One of the primary functions of the heroin disclosed sizing process is. to aid in the reductionof loom abrasion. To do this, the sizing must exert a film forming action, with the resultant film having the ability to resist the abrasive action of the various machine parts that come in contact with the yarns as well as the rubbing together of the individual yarns themselves.

There are many substances which have been in use as warp sizing materials. Thus, aqueous dispersions of starch and many types of starch derivatives are often employed for this purpose. Nevertheless, starch and'the heretofore employed starch derivatives have many shortcomings which the practitioner has longsought to overcome. Starch dispersions, although they are capable of Other sizing agents, such as natural gums and the-newly forming smooth, adhesive films, may, for instance, be

rather unstable and tend to break down or thin out as the result of being continuously maintained at the elevated temperatures required for their application, thereby decreasing their adhesive properties. Some starches tend to form gels upon cooling, which in many cases causes a Wide variation in viscosity due to temperature fluctuations. Such viscosity variations result in poor weaving.

developed synthetic resins, have been found partly suitable, but the lack of uniformity on the part of the natural gums and the high cost of the synthetic resins has precluded the general acceptance of these products. The

introduction of synthetic fabrics woven from nylon, polyester, polyacrylonitrile', and glass fibers, etc., has presented still another problem to the'practitioner since the hydrophobic nature of these synthetics does not permit the ready application of most types of starches which are, of course, hydrophilic. It has therefore been necessary to warp size these synthetics with such substances as polyvinyl alcohol and gelatin, both of which are expensive while gelatin being a natural product is, again nonuniform in character.

This invention comprises the sizing of yarns with a particularclass of substituted starch'derivatives, wherein the substituent radical contains an amine group. Examples'of this type of derivative include both starch esters and others, the only critical requirement being that said starch derivative contain an amine group.

The term starch includes any amylaceous substance such as'untreated starch, as well as starch derivatives including dextrinized, hydrolyzed, oxidized, esterified and etherified starches still retaining amylaceous material. The starches maybe derived from any sources including corn, wheat, potato, tapioca, waxy maize, sago or'rice.

Starch derivatives of the above described type, having notable effects in the warp sizing of textiles, can be made by reacting starch with an esterificatio'n or etherifi'catioh reagent :which will serve to introduce an amine group. Said reagent may be selected from the groupof nitrogen containing compounds consisting of amino alkyl anhydrides, alkyl imines, alkyl epoxides and alkyl amino halides, as well as the corresponding compounds containing. aryl-v groups inaddition to the alkyl groups. All of the various types of reagents listed here, have the cornrn'on characteristic of reacting with hydroxyl groups in the starch to introduce anester or ether linkage, and

thereby introducing an amine radical into the starch.

Representative examples of specific reagents for the purpose of making such starch derivatives include ethylene imine; propylene imine; isatoic anhydride; quinolinic anhydride; b-diethyl amino ethyl chloride; b-methylamino isopropyl chloride; b-dimethyl amino ethyl chloride; 3-diethyl amino 1,2-epoxypropane; 3'-dibutyl amino 1,2-epoxypropane; 2-bromo-5-diethyl amino pentane hydrobromide; N-(2,3-epoxypropyl)-piperidine; and N,N- (2,3-epoxypropyl)methyl aniline. The various halides (e.g. chloro-, bromo-, etc.) can be used interchangeably. In the above reagents, where the free amines have been indicated (e.g.. b-diethyl amino ethyl chloride), one can also use the hydrochloride or other salts of these reagents (e.g. b-diethyl amino ethyl chloride hydrochloride). In fact it is ordinarily preferred to use the salts since these are often less toxic and more convenient to handle. The hydrochloride moiety takes no part in the reaction. It will be seen that besides the alkyL-aryl and aralkyl types, the reagents may also include those containing cyclic groups. Therefore when reference is made tothe-alkyl," aryl and aralkyl' groups, it will be understood that the cyclic reagents are equivalents of these types. In the subsequent examples, it will be noted that the starch-amine reaction .3 product may also be treated so as to result in the quaternary ammonium salt.

Methods for producing the starch-amine derivatives are known. For example, details for making tertiary amino alkyl starch ethers are set forth in US. Patent 2,813,093 which issued on November 12, 1957, and is assigned to the assignees of the subject application. In conducting the warp sizing process of this invention, the use of these tertiary amino alkyl starch ethers is ordinarily preferred.

In making the starch-amine derivatives, starch is preferably treated with any of the previously described reagents, in the presence of an alkaline medium. This may be accomplished by suspending the starch in water, to which has been added (either before or after the addition of the starch) suflicient base, such as alkali metal hydroxide, alkaline earth hydroxide, quaternary ammonium hydroxide, or the like, to maintain the mixture in an alkaline state during the reaction. The required amount of the amine reagent is then added, agitation being maintained until the desired reaction is complete. Heat may be applied, if desired, in order to speed the reaction, since the usual time-temperature relationship appertains. In some cases the alkali may be added stepwise after the addition of the amine reagent, or it may be added simultaneously with the reagent. This latter is the common technique if the reagent is an anhydride.

The proportion of etherification or esterification reagent used will vary with the particular reagent chosen (since they naturally vary in reactivity and reaction eificiency) and the degree of substitution desired. Thus, substantial improvements in warp sizing efiiciency have been achieved by using as an additive an amine-starch derivative made with as little as 0.5% of an amine-introducing reagent, based on the weight of the starch, and on the other hand starch derivatives made with as much as 30% of such a reagent have been successfully employed.

4 may be accomplished by drying the above mentioned gelatinized dispersion over revolving heated drums (or other suitable drying means), or one may take an aqueous suspension of the ungelatinized starch derivative (with or without prior purification by filtration or centrifuging and with or without prior gelatinization as by passing through heated tubes) and convert it to the cold water soluble form by passing over revolving heated drums. In either case, the resulting dry powder has the advantageous property of dispersing in cold water without the necessity of heat. This means, of course, that it may be added directly to water in which the yarns are to undergo sizing, without any pre-cooking of the starch being necessary.

It is well known that starch which in its natural state is in the form of discrete granules, will in the presence of water and sufiicient alkali, undergo gelatinization. The phenomenon of gelatinization involves the swelling, rupture and disintegration of the starch granule, so that it will disperse in water to form a homogeneous hydrated colloidal dispersion, whereas ungelatinized starch granules on the other hand will settle out of water suspension and may be filtered, washed and dried, still retaining their original granule form.

- For use in the warp sizing process, the starch-amine derivatives may be produced either in gelatinized or ungelatinized form.

The advantage of having the derivative in ungelatinized form is that it may be filtered, washed, dried and conveyed to the mill in the form of a dry, pure powder.

In order to avoid gelatinization of the starch during the reaction in those cases where the degree of alkalinity or heat is such as would ordinarily cause gelatinization to occur, one may add a known gelatinization retarding chemical, such as sodium sulfate, to the starch-alkaliwater-reagent mixture. When the amino alkyl starch derivative is supplied to the textile mill in ungelatinized form, it will ordinarily be necessary that the starch productdbe gelatinized, as by cooking in water, before it is use It is also possible to conduct the etherification or esterification reaction in such a manner that the product will be a gelatinized dispersion of the starch-amine derivative in water. This occurs when the alkalinity and/ or heat is suflicient to gelatinize the starch. Even if the starch ether is not gelatinized during the reaction, it may be gelatinized or dispersed simply by heating the reaction mass. The aqueous dispersion of the gelatinized starch derivative may then be used directly for sizing the textile yarns, if desired, with such dilution as may be necessary.

By still another variation, the starch-amine derivative may be produced in dry, cold water soluble form. This It is seen that regardless of which particular physical form of the starch derivative is employed, one is always using in the warp sizing process a starch-amine reaction product which may be broadly described by the following structural formula:

wherein X is a starch, R is a radical selected from the group consisting of substituted alkyl, hydroxyalkyl, acyl, or aroyl radicals, and each of R and R is a radical selected from the group consisting of hydrogen, alkyl, or aralkyl radicals. If the derivative is in the form of the salt, or if it is in the form of the quaternary salt, the formula is then represented as follows:

wherein X is again starch, R is again a radical selected from the group consisting of substituted alkyl, hydroxyalkyl, acyl, or aroyl radicals, and each of R and R is a radical selected from the group consisting of hydrogen, alkyl, or aralkyl radicals, and where R is hydrogen or an alkyl group and Y is a chloride, bromide, or iodide radical.

By introducing an amine group into the starch molecule, a positive electrical charge is established. Efiicient warp sizing is dependent to a large extent on the bond between the size film and the fiber surface, and stronger bonds result from this mutual attraction between the positively charged starch and the negatively charged fiber surfaces. This increased aflinity is displaced with natural fibers as well as with synthetic fibers which, due to their hydrophobic character, ordinarily have a very low degree of attraction for starch derivatives. As a result of this increased adhesion and consequent strengthening of the Warp yarns, a notable increase in weaving efficiency is obtained.

In addition, the use of the herein described starch derivatives aid in reducing the amount of undesirable static electricity generated at the dry end of the sizing process. This static electricity causes the yarns to become attracted to each other, and to become entangled and break, resulting in the loss of much valuable production time. This is such a serious problem with some fibers that cationic lubricants are often added to the sizing in order to help dispel this static charge. However, it has now been found that the selected starch derivatives employed in this process eliminate the need for the addition of these lubricants.

Another advantage derived from the cationic charge inherent in the starch-amine derivatives is their notable resistance towards congealing'of their aqueous dispersions. This brings about improved workability of the sizing in the slasher, more uniform application, and less gelling and lumping, thus leading to a reduction in the clogging of size lines andmechanical breakdowns.

it should also be noted that theuse of thestarch-amine derivatives permits a substantial reduction in the amount of Warp size softener. These softeners, which are usually added to the sizing solution, consist of oleaginous materials which reduce thetendency of the starch dispersion to congeal, and also actas lubricants for the sized yarns. However, these softeners also tend to lessen the film strength of the sizing material; therefore anyreduction in the amount that must be used is advantageous.

The use of a given quantity ofthe starch-amine derivative as a warp size gives results substantially superior to those obtained by the use of relatively larger quantities of the starch sizing materials heretofore known. This not only involves a reduction in cost, but eliminates or minimizes many operational problems, especiallyhigher pickup, which resulted from the use. of the relatively larger quantities of sizing.

In practice, it has been found that starch-amine derivatives can be most effectively used as warp sizing agents when dispersed in water in amounts ranging from 3 to 35 parts of the derivative per hundred parts of water. When warp size softeners are called for in theformulation, no more than 2% of these materials, based upon the weight of the starch-amine derivative, are usually required.

The following examples will illustrate the embodiment of our invention.

Example I-A In this as well as in the subsequent examples, all parts given are by weight unless otherwise indicated.

This example illustrates the treatment of corn starch with b-diethyl amino ethyl chloride hydrochloride, a tertiary amine, to produce a starch derivative for use in our warp sizing process.

Four lbs. sodium hydroxide were dissolved in 150 lbs. water, and 50 lbs. sodiumsulfate were added. Agitation was continued until the reagents had dissolved, and there were then added, with continued agitation, 100 lbs. of corn starch. When the suspension was uniform, there was added a solution of 4 lbs. bdiethyl amino ethyl chloride hydrochloride in 25 lbs. of water. Agitation was maintained for 24 hours, at which time enough dilute hydrochloric acid solution was added to adjust the pH to approximately 3. The starch product was then filtered, washed thoroughly with water and dried.

The resulting starch ether corresponded to the diagrammatic formula:

Example [-3 In this example a starch-amine derivative was made from a thin-boiling corn starch.

Four lbs. calcium hydroxide were dispersed in 150 lbs. water, and there were then added 100 lbs. of a thinboiling corn starch which had been acid converted to a degree known in the trade as 20 fluidity. When the suspension was uniform, there was added a solution of 4 lbs. b-diethyl amino ethyl chloride hydrochloride in 25 lbs. water. Agitation was maintained for 16 hours, at which time the pH was adjusted to 3 by the addition of hydrochloric acid. The starch product was then filtered, washed with water and dried.

Example I-C In this example I repeated the procedure and materials of preceding Example LB, except that in place of the 20 fluidity starch I used a 75 fluidity corn starch, and 6 lbs. of the b-diethyl amino ethyl chloride hydrochloride were employed. Here, too, the final product Was filtered, washed and dried.

Example'I-D Example I-A was repeated, except that the starchamino reaction product was not neutralized, but rather was filtered on the alkaline side, washed'and dried. Thus the final product'contained the freeamine group rather than the amine salt (the salt having beenformedin Example I-A by the neutralization with HCl). The formula of the product of this present example may be diagrammatically represented as follows:

Example I-A was again repeated, except that b-diethyl amino ethyl chloride was used in place of its hydrochloride salt. Aside from the absence of the hydrochloride group, the resulting product was identical to that of Example I-A.

Example IF Example I-G This example is a variation of the'procedure of Example I-A in which a relatively high proportion of amineetherification reagent was used, and the reaction product was gelatinized during the course of the reaction, thereby eliminating any need, on the part of the practitioner, for the heating or redispersal of this product prior to its use in the warp sizing process.

150 lbs. b-diethyl amino ethyl chloride hydrochloride were dissolved in 3,000 lbs. of water. 500 lbs. of tapioca starch were added, and when uniform there were added 400 parts of a 25% aqueous solution of sodium hydroxide. Agitation was maintained continuously, for approximately 10 hours. The pH of the dispersion of the gelatinized starch ether was then adjusted to 5.5-6.5 by the addition of dilute hydrochloric acid.

Example I-H This example illustrates the methods whereby the starch-amine derivative whose preparation was described in Example I-A was converted to the dry, cold water soluble form, thus permitting it to be used in the Warp sizing operation by simply adding to Water, without the necessity for any pre-heating.

A portion of the filtered and washed starch derivative of Example I-A was resuspended in water and gelatinized by passing through a system of heated tubes at superatmospheric pressure (temperature approximately 252 F.). The gelatinization equipment used was that sold by the Girdler Corporation, Louisville, Ky., under the trade name Votator. The gelatinized dispersion Was then dried by passing overrevolving drums, heated at a steam pressure of approximately 125 lbs. per square) over the heated drums in order to simultaneously gelat= inize and dry the product.

7 Example ll-A Twenty parts of the product of Example I-C, along with 0.4 part of a warp size mill wax, as sold by Seydel- Woolley & Co., Atlanta, Ga., under the trade name Seycowax C, were then added to 80 parts of cold water in a heating vessel equipped with an agitator. After five minutes of agitation, or after suchtime as dispersion was complete, heat was applied and the mixture was brought to its boiling point over a 30 minute period. Heating was then continued for an additional 30 minutes. This heated dispersion was then piped into the size box of the slashing apparatus where it was applied to cotton warp yarns according to the procedure described earlier. This sizing procedure was repeated with yarns made from wool, polyester, polyacrylonitrile, rayon and glass filaments, each in turn being sized with the above-described starch ether, the concentrations being varied as found suitable. In all cases where this derivative was used as a sizing agent there were notable improvements in the efficiency of the sizing process as well as in the strength of the sized yarns, as will be seen in subsequent examples.

Example II-B' Three parts of the product of Example I-A were added, along with 0.06 part of Seycowax C, to 97 parts of water and then subjected to the dispersion described above in II-A. The resulting dispersion was utilized in the warp sizing process, with notable improvements being effected in the efficiency of the process as well as in the strength of the resulting yarns.

Example II-C For use in the slashing apparatus 35 parts of the product of Example IC, along with 0.7 part of Seycowax C, were added to 65 parts of water and then subjected to the previously described dispersion procedure. The resulting dispersion was then utilized in the warp sizing process with notable improvements again being effected in both the efficiency of the process and in the strength of the resulting sized yarns.

Example II-D Ten parts of the product of Example I-F, along with 0.2. part of Seycowax C, were added to 90 parts of water and then subjected to the dispersion procedure described in Example I-A. This dispersion was then utilized in the warp sizing process with notable improvements again being effected in both the eiiiciency of the process and in the strength of the resulting sized yarns.

Example III This example illustrates the superior affinity for textile yarns displayed by the cationic starch-amine derivatives.

In a 250 ml. glass beaker, there was prepared 100 ml. of a 0.005% (by Weight) aqueous dispersion of the starchamine derivative of Example I-A. Another 100 ml. dispersion was also prepared, at the same concentration, using in this case an unmodified corn starch. Into each of these dispersions there was totally immersed a one gram strand of Wool yarn, whereupon the dispersions were boiled for three minutes. After cooling, the yarn in each beaker was allowed to drain by hanging over the edge of the beaker, in such a manner that one end of each strand remained immersed in the starch dispersion. A few drops of an iodine solution were then placed upon each strand and into each dispersion.

The strand which had been boiled with the unmodified corn starch dispersion gave a nearly negative starch-iodine test reaction, i.e. it remained white. This indicated, of course, that very little of the starch had been absorbed by the yarn but had, rather, remained in the dispersion, as was further indicated by the very positive test reaction .(i.e. dark blue color) of the dispersion.

On the other hand, the yarn which had been boiled with the cationic starch-amine derivative turned dark blue, while the dispersion itself remained nearly colorless, showing that the yarn had absorbed the starch content of the dispersion.

This test thus indicated the remarkable afiinity which exists betweenthe positively charged starch-amine derivatives and negatively changed yarns. It is this attraction which accounts for the vastly improved results obtained when these derivatives are used as warp sizing agents.

Example IV This example illustrates the superior strength imparted to yarns which have been sized with the starch-amine derivatives used in our process.

In testing the cohesive strength of these yarns, a Duplan cohesion tester, as sold by Geier & Bluhm, Inc., of Troy, New York, was utilized. This device consists of a mechanically propelled friction plate which moves back and forth over the sample of sized yarn which is tightly laced between a series of porcelain hooks. After each back and forth movement, or stroke, of the friction plate, the operator examines the yarn and upon noticing a partial separation, or raveling, the machine is shut off and note is made of the number of strokes which have elapsed. The number of strokes which each sample withstands is thus a direct indication of the cohesive strength of that sample.

The following table gives the results of cohesion tests which were run upon various types of yarns which had been sized with the starch derivative whose preparation and use was illustrated in Example I-A. These results are compared with the results obtained from cohesion tests run upon the same types of yarns which were sized with an unmodified corn starch.

From these results it is obvious that yarns sized with the starch-amine derivatives display a degree of strength far superior to that obtained with ordinary starches.

Example V This example illustrates a test to indicate the reduction in the static electricity charge achieved through the use of the starch-amine derivatives. Comparative anti-static properties of test samples were noted, as revealed by their surface resistance values, a factor which gives a direct indication of the tendency for the development of a static charge.

In this procedure a total of four wool fabric samples were tested. Two of these samples were fabrics which had been finished with the starch-amine derivative of Example I-A, while the remaining two samples were unsized fabrics. These samples were each 1" x 6" and one sample from each pair was cut with its 6" dimension parallel to the selvage of the sample while the other sample from each pair was cut with the 1" dimension parallel to the selvage.

The samples were all conditioned for approximately four hours at a temperature of 74 F. and a relatively humidity of 70%. The surface resistance of each of these samples was then determined, under the same conditions, using a Type H, Teraohmmeter" as sold by the Federal Telephone and Radio Company of Clifton, New Jersey. This device was used at a DC. test potential of volts and an electrification time of one minute, and gave the surface resistance directly in ohms. Three determinations were made upOIl each sample and the average results are presented below.

Average Measured Surface Resistance in hms 10 Sample Wlooiflnished with starch-amine derivative of Example 9 1 Unsizdii b'diiiijjIIIIIlIIIIIIIIIIIIIIIIIIIIIIIIIZIIII 2350 Following the general reaction procedure of Example I-A, there were prepared a number of starch-amine derivatives, using various starches and varying amounts of a number of different amine-introducing reagents. The following table lists the derivatives which were produced.

Percent of Amine Type of Starch Amine Esterifieation or Reagent Undergoing Reaction Etherification Reagent Based on Weight of Starch 1. tapioca b-dimethyl amino isopropyl 3.0

chloride. 2. corn starch acid-conb-dimethyl amino ethyl chlo- 0.5

verted to a degree known ride. in the trade as 60 fluidity. 3. sage 3-dibutyl amino 1,2, epoxy- 10.0

propane. 4. potato z-bromo-fi-diethyl amino pen- 1.0

tane hydrobromlde. 5. waxy maize N532; epoxypropyl) piper- 25.0

me. 6. rice N,N-(2,3epoxypropyl) methyl 30.0

aniline. 7. hydroxyethyl ether of ethylene imlne 35.0

corn starch.

propylene imlne 5. 0 isatoic anhydride... 20. 0 qulnolinic anhydrid 10.0

The above derivatives were also produced in the form of the variations corresponding to those outlined in Examples I-F, G and H (i.e. as the quaternary ammonium salt, in the form of a gelatinized dispersion, and in the form of a dry, cold water soluble powder).

All of these derivatives were then used in the warpsizing of various yarns (e.g. cotton, wool, polyester, polyacrylonitrile, glass filament and rayon). The use of these derivatives resulted in notable improvements in the overall efiiciency of the warp sizing process as well as in the strength of the sized yarns.

Summarizing, this invention teaches the warp-sizing of yarns with cationic starch-amine derivatives. Advantages achieved by the use of these derivatives include increased strength and abrasion resistance of the sized yarns, as well as more eflicient operation of the slashing apparatus. All of these improvements result from the cationic nature of the starch-amine derivatives, which causes them to have an exceptionally high degree of attraction for anionic fibers. While we have herein listed various representative examples of the use of the starch amine derivatives in the warp sizing process, it is understood that many variations in materials, proportions and procedures are possible, without departing from the scope of this invention, as defined in the following claims.

I claim:

1. In a method for the warp sizing of textile yarns, the step which comprises the passage of the yarns through a sizing solution containing a starch-amine reaction product selected from the class consisting of starch-amine reaction products having the following structural formulae:

wherein X is starch, R is a radical selected from the group consisting of substituted alkyl, hydroxyalkyl, acyl, and aroyl radicals, and each of R and R is a radical selected from the group consisting of hydrogen, alkyl, and aralkyl radicals, and where R, is a radical selected from the group consisting of hydrogen and alkyl radicals,

and Y is a radical selected from the group consisting of chloride, bromide, and iodide radicals.

2. The step in the method of claim 1 in which the sizing solution contains from 3 to 35 parts of the starchamine reaction product per parts of water.

3. The method of claim 1, in which the starch-amine reaction product in ungelatinized form is purified and then gelatinized by heating in water before being applied to the textile yarns.

4. The method of claim 1, in which the starch-amine reaction product is in dry, cold water soluble form when added to the sizing bath.

5. The method of claim 1, in which the starch-amine reaction product, when added to the sizing bath, is in the form of a gelatinized dispersion in the original reaction mass.

6. Textile yarns sized with a starch-amine reaction product selected from the class of starch-amine reaction products having the following structural formulae:

wherein X is starch, R is a radical selected from the group consisting of substituted alkyl, hydroxyalkyl, acyl and aroyl radicals, and each of R and R is a radical selected from the group consisting of hydrogen, alkyl and aralkyl radicals, and where R is a radical selected from the group consisting of hydrogen and alkyl radicals, and Y is a radical selected from the group consisting of chloride, bromide and iodide radicals.

References Cited in the file of this patent UNITED STATES PATENTS Yelland Aug. 5, 1952 Caldwell et a1 Nov. 12, 1957 

1. IN A METHOD FOR THE WARP SIZING OF TEXTILE YARNS, THE STEP WHICH COMPRISES THE PASSAGE OF THE YARNS THROUGH A SIZING SOLUTION CONTAINING A STARCH-AMINE REACTION PRODUCT SELECTED FROM THE CLASS CONSISTING OF STARCH-AMINE REACTION PRODUCTS HAVING THE FOLLOWING STRUCTURAL FORMULAE: 